Crystal structure and Hirshfeld analysis of trans-diiodidobis[(methylsulfanyl)benzene-κS]platinum(II)

The title complex represents a further example of a square-planar PtII–dithioether complex. It crystallizes in the monoclinic space group P21/c. Additional Hirshfeld analyses indicate a C—H⋯π interaction along the [010] axis to be the most important packing factor.


Chemical context
Dithioethers are a quite useful class of ligands for various transition-metal complexes and their coordination chemistry is well documented (Murray & Hartley, 1981). As a result of the soft character of the sulfur center, they preferably bond to soft transition metals like the coinage metals (Cu, Ag, Au), mercury(II), or catalytically active noble metals such as rhodium(I), iridium(I), palladium(II) or platinum(II). Apart from structural aspects (Marangoni et al., 1995) and the investigation of inversion dynamics occurring at the coordinated sulfur atoms (Abel et al., 1984), these complexes have been reported to have several applications in homogeneous catalysis (Masdeu-Bulto et al., 2003;Arrayá s & Carretero, 2011). They can form interesting luminescent cluster-like structures (Knorr et al., 2014;Peindy et al., 2007) and even coordination polymers by coordination to Cu I and Ag I (Raghuvanshi et al., 2017;Awaleh et al., 2006). Depending on the metal coordination sphere and the remaining ligands, the preparation of dithioether complexes may yield different isomers. In particular, the isomerism of chalcogenoether complexes with palladium and platinum has been intensively investigated (Vigo et al., 2006) and the presence of both transand cis-isomers in solution and the solid state were proven. The clarification of the trans-cis isomerism is therefore of importance.

trans-Diiodidobis[(methylsulfanyl)benzene-S]platinum(II)
(1) crystallizes from dichloromethane in the monoclinic crystal system, space group P2 1 /c. The molecular structure of 1 is presented in Figs. 2 and 3 and selected bond lengths and bond angles are given in Table 1. The asymmetric unit contains half a molecule of 1, which shows C 2h symmetry. The distance from the coordinating iodine center I1 to Pt1 is 2.61205 (15) Å , showing a slight elongation with respect to its educt structure   Synthesis scheme for trans-PtI 2 (SMePh) 2 ] (1).

Figure 3
Asymmetric unit of 1 with labeled atoms.

Supramolecular features
While a repetition of the molecular structure of 1 can be seen along the [100] axis and the [001] axis, as shown in Fig. 4, the crystal packing along the [010] axis is defined by C-HÁ Á Á interactions of the C2-C7 phenyl ring and H1B i [symmetry code: (i) x, 1 2 À y, À 1 2 + z] with a distance between the phenyl ring and H1B i of 2.5377 (10) Å (Fig. 5). This interaction can also be visualized by a Hirshfeld surface analysis (Spackman & Jayatilaka, 2009) generated by CrystalExplorer21 (Spackman et al., 2021). The Hirshfeld surface mapped over d norm in the range from À0.0074 to 1.1829 a.u. is shown in Fig. 6, with the close contact between H1B i and the C2-C7 plane indicated by the red spot. The contributions of the different types of intermolecular interactions for 1 are shown in the twodimensional fingerprint plots (McKinnon et al., 2007) in Fig. 7. The contribution of the HÁ Á ÁH interactions, with a value of 39.8%, has the largest share of the crystal packing of 1. The remaining hydrogen-heteronuclear interactions have a smaller share with a 15.7% contribution for IÁ Á ÁH, a 14.4% contribution for CÁ Á ÁH and a 3.6% contribution for SÁ Á ÁH. The packing of the solid-state structure of 1 along the [100] axis.

trans-Diiodidobis[(methylsulfanyl)benzene-κS]platinum(II)
Crystal data Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.